1. The electrolyte for the heat-sensitive positive CTP plate is characterized by comprising the following raw materials in parts by weight: 10-20 parts of concentrated hydrochloric acid, 2-4 parts of concentrated sulfuric acid, 2-4 parts of glacial acetic acid, 400 parts of deionized water, 2000 parts of modified auxiliary agent, 10-15 parts of modified additive and 5-7 parts of modified additive;

the modified auxiliary agent is prepared by the following steps:

step S1, uniformly stirring absolute ethyl alcohol and perfluorobutyl sulfonic acid fluorine, adding calcium oxide into the mixture, introducing ammonia gas into the mixture, reacting for 4 to 5 hours, and performing suction filtration, rotary evaporation and drying to obtain an intermediate 1;

step S2, after the intermediate 1, absolute ethyl alcohol and triethylamine are uniformly mixed, perfluorobutyl sulfonyl fluoride is dripped into the mixture under ice bath, reflux reaction is carried out for 6 to 7 hours, the absolute ethyl alcohol is removed by rotary evaporation, dichloromethane is added, stirring is uniformly carried out, triethylamine hydrofluoride is removed by suction filtration, and the intermediate 2 is obtained by drying;

step S3, uniformly stirring glucose and methanol, then dropwise adding ethylenediamine, carrying out reflux reaction for 12h, then placing the mixture under the ice-water bath condition, adding sodium borohydride, carrying out stirring reaction for 2h, then carrying out normal-temperature reaction for 10h, dropwise adding a hydrochloric acid solution to adjust the pH value to 2-3, carrying out suction filtration, washing and drying a filter cake, and thus obtaining an intermediate 3;

step S4, uniformly mixing the intermediate 2, 50 mass percent of sodium hydroxide solution, tetra-n-butylammonium bromide and n-hexane, dropwise adding epichlorohydrin into the mixture, carrying out reflux reaction for 5-7h, extracting the mixture for 2-3 times by using deionized water, and carrying out vacuum distillation on an organic phase to obtain an intermediate 4;

and step S5, uniformly stirring the intermediate 3 and a methanol solution with the mass fraction of 75%, adding the intermediate 4, carrying out reflux reaction for 18-24h at the temperature of 60-75 ℃ in an oil bath, and after the reaction is finished, cooling, carrying out suction filtration, carrying out reduced pressure distillation, washing and recrystallizing to obtain the modification auxiliary agent.

2. The electrolyte for the heat-sensitive positive CTP plate according to claim 1, wherein the electrolyte comprises: the dosage ratio of the absolute ethyl alcohol, the perfluorobutyl sulfonic acid fluoride, the calcium oxide and the ammonia gas in the step S1 is 33-35 mL: 1.1-1.3 mol: 0.12-0.13 mol: 3-4 mol.

3. The electrolyte for the heat-sensitive positive CTP plate according to claim 1, wherein the electrolyte comprises: the dosage ratio of the intermediate 1, the absolute ethyl alcohol, the triethylamine, the perfluorobutanesulfonyl fluoride and the dichloromethane in the step S2 is 1 mol: 43-45 mL: 0.3-0.4 mol: 1 mol: 13-15 mL.

4. The electrolyte for the heat-sensitive positive CTP plate according to claim 1, wherein the electrolyte comprises: the dosage ratio of the glucose, the methanol, the ethylenediamine and the sodium borohydride in the step S3 is 102-106 mmol: 140-145 mL: 48-51 mmol: 123-128 mmol.

5. The electrolyte for the heat-sensitive positive CTP plate according to claim 1, wherein the electrolyte comprises: step S4, the dosage ratio of the intermediate 2, the sodium hydroxide solution, the tetra-n-butylammonium bromide, the n-hexane and the epichlorohydrin is 30-33 mmol: 40-44 mmol: 1.5-1.7 mmol: 130-140 mL: 35-40 mmol.

6. The electrolyte for the heat-sensitive positive CTP plate according to claim 1, wherein the electrolyte comprises: the dosage ratio of the intermediate 3, the methanol solution and the intermediate 4 in the step S5 is 16-18 mmol: 142 and 146 mL: 50-53 mmol.

7. The method for preparing the electrolyte for the heat-sensitive positive CTP plate according to claim 1, wherein the electrolyte comprises: the preparation method comprises the following preparation steps:

uniformly mixing concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid and deionized water at 0 ℃, adding a modification auxiliary agent and a modification additive, and uniformly stirring to obtain the electrolyte for the heat-sensitive positive CTP plate.

Background

The CTP technology is that image information on a computer can be directly transmitted to a plate material, a link of film production in the middle is omitted, and the CTP plate is an updated product of a conventional PS plate. The CTP plate consists of a plate base and a photosensitive layer, wherein the plate base is commercially pure aluminum of A1050 and H18. The plate-based processing generally includes the following processes: the method comprises the steps of deoiling, electrolysis, ash removal, oxidation, hole sealing and the like, wherein the electrolysis has a crucial influence on the performance of the CTP plate, the electrolysis is a process for generating grains, the generated grain forms are different due to different electrolysis processes, and the sensitivity, the printing resistance, the plate base density and the ink balance in the printing process of the CTP plate are directly influenced by the quality of the grain forms.

Referring to Chinese patent CN101872125A, a new electrolysis process of CTP plate base is disclosed, which has the scheme that: the use requirement of the CTP plate base can be met by adding alkali washing and water washing in the electrolytic process and using a single HCl solution as an electrolyte, wherein the HCl concentration in the electrolyte is 1.4-2.0%, and the alkali washing process comprises the following steps: 0.5-1.5% NaOH solution, the alkali washing time is 10-60s, the alkali washing temperature is 20-30 ℃, and the water washing process comprises the following steps: the water washing flow is more than 100L/min, the flow rate is more than 3m/s, the water washing time is 10-60s, the electrolysis process is cheap and easy to control stably, but the surface tension of the electrolyte and aluminum is large in the electrolysis process, the wettability is poor, the shape of grains is uneven, the surface is rough, and meanwhile, large pits or platforms can appear along with the gradual increase of the corrosion rate to cause defective products.

Disclosure of Invention

The invention aims to provide an electrolyte for a heat-sensitive positive CTP plate and a preparation method thereof.

The problems to be solved by the invention are as follows: the electrolyte and aluminum have large surface tension and poor wettability in the electrolytic process, so that the shape of grains is uneven, the surface is rough, and meanwhile, large pits or platforms can appear along with the gradual increase of the corrosion rate to cause inferior-quality products.

The purpose of the invention can be realized by the following technical scheme:

an electrolyte for a heat-sensitive positive CTP plate comprises the following raw materials in parts by weight:

10-20 parts of concentrated hydrochloric acid, 2-4 parts of concentrated sulfuric acid, 2-4 parts of glacial acetic acid, 400 parts of deionized water, 2000 parts of modified auxiliary agent, 10-15 parts of modified additive and 5-7 parts of modified additive;

the electrolyte for the heat-sensitive positive CTP plate is prepared by the following steps:

uniformly mixing concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid and deionized water at 0 ℃, adding a modification auxiliary agent and a modification additive, and uniformly stirring to obtain the electrolyte for the heat-sensitive positive CTP plate.

The modified auxiliary agent is prepared by the following steps:

step S1, adding absolute ethyl alcohol and perfluorobutyl sulfonic acid fluorine into a three-neck flask, uniformly stirring, adding calcium oxide, introducing ammonia gas at the rotation speed of 220-70 rpm, reacting for 4-5h, performing suction filtration and rotary evaporation, and drying in an oven at 60-70 ℃ for 3-4h to obtain an intermediate 1;

the reaction process is as follows:

step S2, adding the intermediate 1, absolute ethyl alcohol and triethylamine into a three-neck flask, dripping perfluorobutyl sulfonyl fluoride under ice bath, after dripping, carrying out reflux reaction for 6-7h, carrying out rotary evaporation to remove the absolute ethyl alcohol, adding dichloromethane, stirring uniformly, carrying out suction filtration to remove triethylamine hydrofluoride, and drying at 70-75 ℃ for 3-4h to obtain an intermediate 2;

the reaction process is as follows:

step S3, adding glucose and methanol into a three-neck flask, stirring uniformly, slowly adding ethylene diamine dropwise, performing reflux reaction for 12 hours, then placing under an ice-water bath condition, adding sodium borohydride into the mixture, stirring for reaction for 2 hours, then reacting at normal temperature for 10 hours, after the reaction is finished, adding a hydrochloric acid solution with the mass fraction of 35% dropwise to adjust the pH value to 2-3, performing suction filtration, washing a filter cake for 3 times by using ice water and ice-methanol, and naturally drying to obtain an intermediate 3;

the reaction process is as follows:

step S4, adding the intermediate 2, a sodium hydroxide solution with the mass fraction of 50%, tetra-n-butylammonium bromide and n-hexane into a three-neck flask, slowly dripping epichlorohydrin into the three-neck flask under the conditions of controlling the temperature to be 30-40 ℃ and the rotation speed of 230-250rpm, carrying out reflux reaction for 5-7h, extracting the mixture for 2-3 times by using deionized water after the reaction is finished, and carrying out vacuum distillation on an organic phase to obtain an intermediate 4;

the reaction process is as follows:

and step S5, adding the intermediate 3 and a methanol solution with the mass fraction of 75% into a three-neck flask, uniformly stirring, adding the intermediate 4, carrying out reflux reaction for 18-24h under an oil bath at the temperature of 60-75 ℃, cooling, carrying out suction filtration and reduced pressure distillation to remove the methanol solution after the reaction is finished, washing for 2-3 times by using n-hexane, and recrystallizing by using acetone to obtain the modification aid.

The reaction process is as follows:

further, in the step S1, the dosage ratio of the absolute ethyl alcohol, the perfluorobutyl sulfonic acid fluoride, the calcium oxide and the ammonia gas is 33-35 mL: 1.1-1.3 mol: 0.12-0.13 mol: 3-4 mol.

Further, the using amount ratio of the intermediate 1, anhydrous ethanol, triethylamine, perfluorobutanesulfonyl fluoride and dichloromethane in the step S2 is 1 mol: 43-45 mL: 0.3-0.4 mol: 1 mol: 13-15 mL.

Further, in step S3, the dosage ratio of glucose, methanol, ethylenediamine and sodium borohydride is 102-106 mmol: 140-145 mL: 48-51 mmol: 123-128 mmol.

Further, the using ratio of the intermediate 2, the sodium hydroxide solution, the tetra-n-butylammonium bromide, the n-hexane and the epichlorohydrin in the step S4 is 30-33 mmol: 40-44 mmol: 1.5-1.7 mmol: 130-140 mL: 35-40 mmol.

Further, the using ratio of the intermediate 3, the methanol solution and the intermediate 4 in the step S5 is 16-18 mmol: 142 and 146 mL: 50-53 mmol.

Wherein the modified additive is prepared by the following steps:

step C1, adding isopropanol, deionized water and starch into a three-neck flask, uniformly stirring, adding chloroacetic acid, cooling to 10 ℃, controlling the temperature to be within 20min, adding sodium hydroxide into the three-neck flask, heating to 25 ℃, stirring for 30min, performing reflux reaction for 4-5h, adding glacial acetic acid for neutralization, washing for 2-3 times by using a methanol solution with the mass fraction of 70%, and drying for 3-4h at 70-75 ℃ to obtain an intermediate 5;

the reaction process is as follows:

and step C2, dissolving the intermediate 5 in formamide, dropwise adding a formamide solution of chlorosulfonic acid into the formamide solution at the temperature of 5-8 ℃ to react for 2-3h, separating out a product by using acetone, washing the product for 2-3 times by using a 0.1mol/L sodium hydroxide solution, washing the product for 1-2 times by using acetone, and drying the product for 4-5h at the temperature of 70-75 ℃ to obtain the modified additive.

The reaction process is as follows:

further, in the step C1, the dosage ratio of the isopropanol, the deionized water, the starch, the chloroacetic acid and the sodium hydroxide is 123-126 mL: 5-7 mL: 22-25 g: 11-13 mL: 0.5-1 g.

Further, the dosage ratio of the intermediate 5, formamide and chlorosulfonic acid in the formamide solution in the step C2 is 5.2-6.1 g: 35-40 mL: 13.5-14.2mL, wherein the mass ratio of the chlorosulfonic acid to the formamide in the formamide solution of the chlorosulfonic acid is 1: 3.

a preparation method of an electrolyte for a heat-sensitive positive CTP plate comprises the following steps:

uniformly mixing concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid and deionized water at 0 ℃, adding a modification auxiliary agent and a modification additive, and uniformly stirring to obtain the electrolyte for the heat-sensitive positive CTP plate.

The invention has the beneficial effects that: the invention aims to provide an electrolyte for a heat-sensitive positive CTP plate and a preparation method thereof, the electrolyte is used for a process of generating sand meshes on the surface of an aluminum plate, the aluminum plate is soaked in the electrolyte, alternating current is applied to aluminum, and the aluminum generates Al → Al in the positive half cycle³⁺Negative half cycle generation of H⁺→H₂The steps are alternately repeated, so that small corrosion pits are formed on the surface of the aluminum, but the electrolyte and the aluminum have large surface tension and poor wettability in the electrolytic process, so that the shape of a grain is uneven, the surface is rough, and meanwhile, a large pit or a platform can appear along with the gradual increase of the corrosion rate to cause defective products, so that a modification auxiliary agent and a modification additive are added into the electrolyte to play a role in inhibiting corrosion, so that the corrosion uniformity is ensured, the yield is improved, the defective rate is lower than 3 per thousand, the modification auxiliary agent is prepared by organic synthesis, perfluorobutyl sulfonic acid fluorine reacts with ammonia gas to generate an intermediate 1, the intermediate 1 reacts with perfluorobutyl sulfonyl fluoride to generate an intermediate 2, glucose reacts with ethylene diamine to generate an intermediate 3, the intermediate 2 reacts with epoxy chloropropane to generate an intermediate 4, the intermediate 3 reacts with the intermediate 4 to generate the modification auxiliary agent, and the modification auxiliary agent is used as an amphiphilic surfactant, the hydrophobic end of the fluorine-containing group faces to the surface of aluminum, and polar groups such as hydroxyl groups, sulfonic acid groups and the likeThe clusters face a water interface to reduce the surface tension of the electrolyte and aluminum and improve the wettability, meanwhile, the electrical property carried by polyhydroxy in a glucose molecular structure can also adjust the corrosion rate of the electrolyte in time to play a corrosion inhibition effect, oxygen atoms in hydroxyl groups are electronegative, aluminum is positively charged in the electrolysis process, glucose molecules are adsorbed on the positively charged aluminum surface through the hydroxyl groups with electronegativity in the structure, and chemical adsorption can be formed between the aluminum atoms and the oxygen atoms, so that the activity of aluminum active points is reduced, the corrosion rate is slowed down, the corrosion uniformity is ensured, and the sand surface is smooth and flat; in addition, the modified additive is modified anionic starch, firstly, the starch is modified, anionic carboxyl and sulfonic group are introduced, the starch derivative is endowed with solubility and high viscosity in cold water, when the electrolyte is prepared at the temperature of 0 ℃, the starch can be fully dissolved, secondly, the introduction of the anionic group can be combined with aluminum with positive charge, the activity of an aluminum active point is reduced, the corrosion rate is slowed down, and the synergistic effect of the modified additive and the modified additive enables the aluminum surface to be fine and smooth, the sand mesh area to be flat and have fine crystals and complete appearance.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The modified auxiliary agent is prepared by the following steps:

step S1, adding 33mL of absolute ethyl alcohol and 1.1mol of perfluorobutyl sulfonic acid fluorine into a three-neck flask, uniformly stirring, adding 0.12mol of calcium oxide, introducing 3mol of ammonia gas at a rotating speed of 220rpm, reacting for 4 hours, performing suction filtration and rotary evaporation, and drying in an oven at 60 ℃ for 3 hours to obtain an intermediate 1;

step S2, adding 1mol of intermediate 1, 43mL of anhydrous ethanol and 0.3mol of triethylamine into a three-neck flask, dropwise adding 1mol of perfluorobutylsulfonyl fluoride under ice bath, after dropwise adding, carrying out reflux reaction for 6h, carrying out rotary evaporation to remove the anhydrous ethanol, adding 13mL of dichloromethane, stirring uniformly, carrying out suction filtration to remove triethylamine hydrofluoride, and drying at 70 ℃ for 3h to obtain an intermediate 2;

step S3, adding 102mmol of glucose and 140mL of methanol into a three-neck flask, stirring uniformly, slowly adding 48mmol of ethylenediamine dropwise, carrying out reflux reaction for 12 hours, then placing under an ice-water bath condition, adding 123mmol of sodium borohydride, stirring for reaction for 2 hours, then carrying out normal-temperature reaction for 10 hours, after the reaction is finished, adding a hydrochloric acid solution with the mass fraction of 35% to adjust the pH value to 2, carrying out suction filtration, washing a filter cake for 3 times by using ice water and ice methanol, and naturally drying to obtain an intermediate 3;

step S4, adding 30mmol of intermediate 2, 40mmol of sodium hydroxide solution with mass fraction of 50%, 1.5mmol of tetra-n-butylammonium bromide and 130mL of n-hexane into a three-neck flask, slowly dropwise adding 35mmol of epichlorohydrin into the three-neck flask under the conditions of 30 ℃ and 230rpm of rotation speed, carrying out reflux reaction for 5 hours, extracting the mixture for 2 times by using deionized water after the reaction is finished, and carrying out vacuum distillation on an organic phase to obtain an intermediate 4;

and step S5, adding 16mmol of intermediate 3 and 142mL of methanol solution with the mass fraction of 75% into a three-neck flask, uniformly stirring, adding 50mmol of intermediate 4, carrying out reflux reaction for 18h under an oil bath at 60 ℃, cooling, carrying out suction filtration and reduced pressure distillation to remove the methanol solution after the reaction is finished, washing for 2 times by using n-hexane, and recrystallizing by using acetone to obtain the modification auxiliary agent.

Example 2

The modified auxiliary agent is prepared by the following steps:

step S1, adding 34mL of absolute ethyl alcohol and 1.2mol of perfluorobutyl sulfonic acid fluorine into a three-neck flask, uniformly stirring, adding 0.12mol of calcium oxide, introducing 3.5mol of ammonia gas at the rotating speed of 235rpm, reacting for 4 hours, performing suction filtration and rotary evaporation, and drying in an oven at 65 ℃ for 3 hours to obtain an intermediate 1;

step S2, adding 1mol of intermediate 1, 44mL of anhydrous ethanol and 0.35mol of triethylamine into a three-neck flask, dropwise adding 1mol of perfluorobutylsulfonyl fluoride under ice bath, after dropwise adding, carrying out reflux reaction for 6h, carrying out rotary evaporation to remove the anhydrous ethanol, adding 14mL of dichloromethane, stirring uniformly, carrying out suction filtration to remove triethylamine hydrofluoride, and drying at 72 ℃ for 3h to obtain an intermediate 2;

step S3, adding 104mmol of glucose and 142mL of methanol into a three-neck flask, stirring uniformly, slowly adding 49mmol of ethylenediamine dropwise, performing reflux reaction for 12 hours, placing under an ice-water bath condition, adding 125mmol of sodium borohydride, stirring for reaction for 2 hours, then reacting at normal temperature for 10 hours, after the reaction is finished, adding a hydrochloric acid solution with the mass fraction of 35% to adjust the pH value to 2, performing suction filtration, washing a filter cake for 3 times by using ice water and ice methanol, and naturally drying to obtain an intermediate 3;

step S4, adding 32mmol of intermediate 2, 42mmol of sodium hydroxide solution with mass fraction of 50%, 1.6mmol of tetra-n-butylammonium bromide and 135mL of n-hexane into a three-neck flask, slowly dropwise adding 38mmol of epoxy chloropropane into the three-neck flask under the conditions of 35 ℃ and rotation speed of 240rpm, carrying out reflux reaction for 6 hours, extracting the mixture for 2 times by using deionized water after the reaction is finished, and carrying out vacuum distillation on an organic phase to obtain an intermediate 4;

and step S5, adding 17mmol of intermediate 3 and 144mL of methanol solution with the mass fraction of 75% into a three-neck flask, uniformly stirring, adding 51mmol of intermediate 4, carrying out reflux reaction for 20 hours at 70 ℃ in an oil bath, cooling, carrying out suction filtration and reduced pressure distillation after the reaction is finished to remove the methanol solution, washing for 2 times by using n-hexane, and recrystallizing by using acetone to obtain the modification aid.

Example 3

The modified auxiliary agent is prepared by the following steps:

step S1, adding 35mL of absolute ethyl alcohol and 1.3mol of perfluorobutyl sulfonic acid fluorine into a three-neck flask, uniformly stirring, adding 0.13mol of calcium oxide, introducing 4mol of ammonia gas at the rotating speed of 250rpm, reacting for 5 hours, performing suction filtration and rotary evaporation, and drying in an oven at 70 ℃ for 4 hours to obtain an intermediate 1;

step S2, adding 1mol of intermediate 1, 45mL of anhydrous ethanol and 0.4mol of triethylamine into a three-neck flask, dropwise adding 1mol of perfluorobutylsulfonyl fluoride under ice bath, after dropwise adding, carrying out reflux reaction for 7h, carrying out rotary evaporation to remove the anhydrous ethanol, adding 15mL of dichloromethane, stirring uniformly, carrying out suction filtration to remove triethylamine hydrofluoride, and drying at 75 ℃ for 4h to obtain an intermediate 2;

step S3, adding 106mmol of glucose and 145mL of methanol into a three-neck flask, stirring uniformly, slowly adding 51mmol of ethylenediamine dropwise, carrying out reflux reaction for 12 hours, then placing under an ice-water bath condition, adding 128mmol of sodium borohydride, stirring for reaction for 2 hours, then reacting at normal temperature for 10 hours, after the reaction is finished, adding 35% by mass of hydrochloric acid solution dropwise to adjust the pH value to 3, carrying out suction filtration, washing a filter cake for 3 times by using ice water and ice methanol, and naturally drying to obtain an intermediate 3;

step S4, adding 33mmol of intermediate 2, 44mmol of sodium hydroxide solution with mass fraction of 50%, 1.7mmol of tetra-n-butylammonium bromide and 140mL of n-hexane into a three-neck flask, slowly dropwise adding 40mmol of epoxy chloropropane into the three-neck flask under the conditions of 40 ℃ and rotation speed of 250rpm, carrying out reflux reaction for 7 hours, extracting the mixture for 3 times by using deionized water after the reaction is finished, and carrying out vacuum distillation on an organic phase to obtain an intermediate 4;

and step S5, adding 18mmol of intermediate 3 and 146mL of methanol solution with the mass fraction of 75%, uniformly stirring, adding 53mmol of intermediate 4, carrying out reflux reaction for 24 hours at 75 ℃ in an oil bath, cooling, carrying out suction filtration and reduced pressure distillation to remove the methanol solution after the reaction is finished, washing for 3 times by using n-hexane, and recrystallizing by using acetone to obtain the modification aid.

Example 4

The modified additive is prepared by the following steps:

step C1, adding 123mL of isopropanol, 5mL of deionized water and 22g of starch into a three-neck flask, uniformly stirring, adding 11mL of chloroacetic acid, cooling to 10 ℃, controlling the temperature to be within 20min, adding 0.5g of sodium hydroxide, heating to 25 ℃, stirring for 30min, carrying out reflux reaction for 4h, adding glacial acetic acid for neutralization, washing for 2 times by using a methanol solution with the mass fraction of 70%, and drying for 3h at 70 ℃ to obtain an intermediate 5;

and step C2, dissolving 5.2g of the intermediate 5 in 35mL of formamide, dropwise adding 13.5mL of formamide solution of chlorosulfonic acid into the formamide solution at the temperature of 5 ℃, reacting for 2 hours, washing a product with 0.1mol/L sodium hydroxide solution for 2 times after the product is separated out by acetone, then washing the product with acetone for 1 time, and drying the product at the temperature of 70 ℃ for 4 hours to obtain the modified additive, wherein the mass ratio of chlorosulfonic acid to formamide in the formamide solution of chlorosulfonic acid is 1: 3.

example 5

The modified additive is prepared by the following steps:

step C1, adding 124mL of isopropanol, 6mL of deionized water and 23g of starch into a three-neck flask, uniformly stirring, adding 12mL of chloroacetic acid, cooling to 10 ℃, controlling the temperature to be within 20min, adding 0.7g of sodium hydroxide, heating to 25 ℃, stirring for 30min, carrying out reflux reaction for 4h, adding glacial acetic acid for neutralization, washing for 2 times by using a methanol solution with the mass fraction of 70%, and drying for 3h at 70 ℃ to obtain an intermediate 5;

and step C2, dissolving 58g of intermediate 5 in 38mL of formamide, dropwise adding 13.8mL of formamide solution of chlorosulfonic acid into the formamide solution at 6 ℃ for reaction for 2 hours, washing a product with 0.1mol/L sodium hydroxide solution for 2 times after the product is separated out by acetone, then washing the product with acetone for 1 time, and drying the product at 72 ℃ for 4 hours to obtain the modified additive, wherein the mass ratio of chlorosulfonic acid to formamide in the formamide solution of chlorosulfonic acid is 1: 3.

example 6

The modified additive is prepared by the following steps:

step C1, adding 126mL of isopropanol, 7mL of deionized water and 25g of starch into a three-neck flask, uniformly stirring, adding 13mL of chloroacetic acid, cooling to 10 ℃, controlling the temperature to be within 20min, adding 1g of sodium hydroxide, heating to 25 ℃, stirring for 30min, carrying out reflux reaction for 5h, adding glacial acetic acid for neutralization, washing for 3 times by using a methanol solution with the mass fraction of 70%, and drying for 4h at 75 ℃ to obtain an intermediate 5;

and step C2, dissolving 6.1g of intermediate 5 in 40mL of formamide, dropwise adding 14.2mL of formamide solution of chlorosulfonic acid into the formamide solution at the temperature of 8 ℃, reacting for 3 hours, washing a product with 0.1mol/L sodium hydroxide solution for 3 times after the product is separated out by acetone, then washing the product with acetone for 2 times, and drying the product at the temperature of 5 ℃ for 5 hours to obtain the modified additive, wherein the mass ratio of chlorosulfonic acid to formamide in the formamide solution of chlorosulfonic acid is 1: 3.

example 7

An electrolyte for a heat-sensitive positive CTP plate comprises the following raw materials in parts by weight:

10 parts of concentrated hydrochloric acid, 2 parts of concentrated sulfuric acid, 2 parts of glacial acetic acid, 400 parts of deionized water, 10 parts of a modification auxiliary agent and 5 parts of a modification additive;

the electrolyte for the heat-sensitive positive CTP plate is prepared by the following steps:

and (2) uniformly mixing concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid and deionized water at 0 ℃, adding the modification auxiliary agent prepared in the step 1 and the modification additive prepared in the step 4, and uniformly stirring to obtain the electrolyte for the heat-sensitive positive CTP plate.

Example 8

An electrolyte for a heat-sensitive positive CTP plate comprises the following raw materials in parts by weight:

15 parts of concentrated hydrochloric acid, 3 parts of concentrated sulfuric acid, 3 parts of glacial acetic acid, 800 parts of deionized water, 12 parts of a modification auxiliary agent and 6 parts of a modification additive;

the electrolyte for the heat-sensitive positive CTP plate is prepared by the following steps:

and (3) uniformly mixing concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid and deionized water at 0 ℃, adding the modification auxiliary agent prepared in the step (2) and the modification additive prepared in the step (5), and uniformly stirring to obtain the electrolyte for the heat-sensitive positive CTP plate.

Example 9

An electrolyte for a heat-sensitive positive CTP plate comprises the following raw materials in parts by weight:

20 parts of concentrated hydrochloric acid, 4 parts of concentrated sulfuric acid, 4 parts of glacial acetic acid, 2000 parts of deionized water, 15 parts of a modification auxiliary agent and 7 parts of a modification additive;

the electrolyte for the heat-sensitive positive CTP plate is prepared by the following steps:

and (3) uniformly mixing concentrated hydrochloric acid, concentrated sulfuric acid, glacial acetic acid and deionized water at 0 ℃, adding the modification auxiliary agent prepared in the step (3) and the modification additive prepared in the step (6), and uniformly stirring to obtain the electrolyte for the heat-sensitive positive CTP plate.

Comparative example 1

The electrolyte of comparative example 1 was prepared by referring to example 7 except that no modification aid was added.

Comparative example 2

The electrolyte of comparative example 2 was prepared according to example 7, except that no modifying additive was added.

Comparative example 3

The electrolyte of comparative example 3 was prepared by referring to example 7 except that the modification assistant and the modification additive were not added.

Example 10

The CTP plate base is respectively put into the electrolyte prepared in the examples 7-9 and the comparative examples 1-3 for multi-stage electrolysis, the electrolytic voltage is 9V, the current is 1.2KA, the electrolyte temperature is 20 ℃, the surface appearance of the CTP plate base after corrosion is tested, and the test data is shown in Table 1:

as can be seen from Table 1, compared with the comparative example, the electrolytic corrosion performance of the electrolyte prepared by the method is more excellent, and under the synergistic effect of the modification additive and the modification additive, the CTP plate base has small hole size, regular shape, dense and uniform distribution and smooth surface.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.